TW202334318A - Curable silicone composition - Google Patents
Curable silicone composition Download PDFInfo
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- TW202334318A TW202334318A TW112102821A TW112102821A TW202334318A TW 202334318 A TW202334318 A TW 202334318A TW 112102821 A TW112102821 A TW 112102821A TW 112102821 A TW112102821 A TW 112102821A TW 202334318 A TW202334318 A TW 202334318A
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- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 111
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 39
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 33
- 125000003118 aryl group Chemical group 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 7
- -1 polysiloxane Polymers 0.000 claims description 112
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- 239000002683 reaction inhibitor Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 230000009974 thixotropic effect Effects 0.000 abstract description 28
- 229910020485 SiO4/2 Chemical group 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000003961 organosilicon compounds Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GFKCWAROGHMSTC-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexyl)silane Chemical compound CO[Si](OC)(OC)CCCCCC[Si](OC)(OC)OC GFKCWAROGHMSTC-UHFFFAOYSA-N 0.000 description 2
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- KSLSOBUAIFEGLT-UHFFFAOYSA-N 2-phenylbut-3-yn-2-ol Chemical compound C#CC(O)(C)C1=CC=CC=C1 KSLSOBUAIFEGLT-UHFFFAOYSA-N 0.000 description 1
- HMVBQEAJQVQOTI-UHFFFAOYSA-N 3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)C=C(C)C#C HMVBQEAJQVQOTI-UHFFFAOYSA-N 0.000 description 1
- GRGVQLWQXHFRHO-UHFFFAOYSA-N 3-methylpent-3-en-1-yne Chemical compound CC=C(C)C#C GRGVQLWQXHFRHO-UHFFFAOYSA-N 0.000 description 1
- PBYDIWCXDGMNRO-UHFFFAOYSA-N 3-trimethoxysilylpropyl but-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=CC PBYDIWCXDGMNRO-UHFFFAOYSA-N 0.000 description 1
- 101000795655 Canis lupus familiaris Thymic stromal cotransporter homolog Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本發明係關於一種可固化聚矽氧組成物。The invention relates to a curable polysiloxane composition.
可固化聚矽氧組成物包含：由(CH 3) 3SiO 1/2單元、CH 2=CH(CH 3)SiO 2/2單元、及SiO 4/2單元組成之有機聚矽氧烷樹脂；在分子中具有至少兩個矽原子鍵結氫原子的有機聚矽氧烷；及矽氫化反應催化劑之可固化聚矽氧組成物，該可固化聚矽氧組成物固化以形成具有極佳耐熱性、電絕緣特性及耐候性之透明固化產物。因此，可固化聚矽氧組成物被廣泛用作電/電子設備之保護性塗層劑、封裝材料或密封劑。在一特定應用中，需要可固化聚矽氧組成物之觸變特性，以控制流動性且在其分配後保持其形狀。 The curable polysiloxane composition includes: an organic polysiloxane resin composed of (CH 3 ) 3 SiO 1/2 units, CH 2 =CH(CH 3 )SiO 2/2 units, and SiO 4/2 units; An organic polysiloxane having at least two silicon atoms bonded to hydrogen atoms in the molecule; and a curable polysiloxane composition of a silicon hydrogenation reaction catalyst that is cured to form a polysiloxane with excellent heat resistance , transparent cured product with electrical insulation properties and weather resistance. Therefore, curable polysiloxane compositions are widely used as protective coating agents, encapsulating materials or sealants for electrical/electronic equipment. In one particular application, the thixotropic properties of the curable polysiloxane composition are required to control flow and maintain its shape after it is dispensed.
舉例而言，專利文件1於實例1中揭示可固化聚矽氧組成物，其包含：由CH 2=CH(CH 3) 2SiO 1/2單元、(CH 3) 3SiO 1/2單元、及SiO 4/2單元組成之有機聚矽氧烷樹脂；乙烯基封端之二甲基聚矽氧烷；甲基氫聚矽氧烷；及鉑催化劑。專利文件1亦揭示，在不損害透明度之範圍內，諸如煙霧二氧化矽之無機填料用於增強強度。然而，專利文件1不關於增強可固化聚矽氧組成物之觸變特性。 For example, Patent Document 1 discloses a curable polysiloxane composition in Example 1, which includes: CH 2 =CH(CH 3 ) 2 SiO 1/2 units, (CH 3 ) 3 SiO 1/2 units, Organopolysiloxane resin composed of SiO 4/2 units; vinyl-terminated dimethylpolysiloxane; methyl hydrogen polysiloxane; and platinum catalyst. Patent Document 1 also discloses that inorganic fillers such as fumed silica are used to enhance strength within the scope of not impairing transparency. However, Patent Document 1 does not relate to enhancing the thixotropic properties of the curable polysiloxane composition.
專利文件2於實例4中揭示可固化聚矽氧組成物，其包含：在兩個分子鏈端處用二甲基乙烯基矽氧基封端之二甲基矽氧烷及甲基乙烯基矽氧烷之共聚物；由CH 2=CH(CH 3) 2SiO 1/2單元、(CH 3) 3SiO 1/2單元、及SiO 4/2單元組成之有機聚矽氧烷樹脂；由(CH 3) 2HSiO 1/2單元及SiO 4/2單元組成之甲基氫聚矽氧烷；鉑催化劑；及煙霧二氧化矽。然後，可固化聚矽氧組成物固化形成低透明固化產物。專利文件2亦於實例5中揭示可固化聚矽氧組成物，其包含：在兩個分子鏈端處用二甲基乙烯基矽氧基封端之二甲基矽氧烷及二苯基矽氧烷之共聚物；由CH 2=CH(CH 3) 2SiO 1/2單元、(CH 3) 3SiO 1/2單元、及SiO 4/2單元組成之有機聚矽氧烷樹脂；由(CH 3) 2HSiO 1/2單元及SiO 4/2單元組成之甲基氫聚矽氧烷；及鉑催化劑。然而，專利文件2不關於增強可固化聚矽氧組成物之觸變特性。 Patent Document 2 discloses a curable polysiloxane composition in Example 4, which includes: dimethylsiloxane and methylvinylsiloxane terminated with dimethylvinylsiloxy groups at two molecular chain ends. Copolymer of oxalane; organic polysiloxane resin composed of CH 2 =CH(CH 3 ) 2 SiO 1/2 units, (CH 3 ) 3 SiO 1/2 units, and SiO 4/2 units; composed of ( Methyl hydrogen polysiloxane composed of CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units; platinum catalyst; and fumed silica. Then, the curable polysiloxane composition is cured to form a low-transparency cured product. Patent Document 2 also discloses a curable polysiloxane composition in Example 5, which includes: dimethylsiloxane and diphenylsiloxane terminated with dimethylvinylsiloxy groups at two molecular chain ends. Copolymer of oxalane; organic polysiloxane resin composed of CH 2 =CH(CH 3 ) 2 SiO 1/2 units, (CH 3 ) 3 SiO 1/2 units, and SiO 4/2 units; composed of ( Methyl hydrogen polysiloxane composed of CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units; and platinum catalyst. However, Patent Document 2 does not relate to enhancing the thixotropic properties of the curable polysiloxane composition.
專利文件3於實例1中揭示可固化聚矽氧組成物，其包含：在兩個分子鏈端處用三乙烯基矽氧基封端之二甲基矽氧烷及二苯基矽氧烷之共聚物；由CH 2=CH(CH 3) 2SiO 1/2單元、(CH 3) 3SiO 1/2單元、及SiO 4/2單元組成之有機聚矽氧烷樹脂；由(CH 3) 2HSiO 1/2單元及SiO 4/2單元組成之聚甲基氫矽氧烷；在兩個分子鏈端處用三甲基矽氧基封端之甲基氫聚矽氧烷；鉑催化劑；煙霧二氧化矽；及作為觸變賦予劑之具有環氧丙氧基丙基之有機聚矽氧烷。可固化聚矽氧組成物固化以形成透明固化產物，但與使用在兩個分子鏈端處用二甲基乙烯基矽氧基封端之二甲基聚矽氧烷代替二甲基矽氧烷及二苯基矽氧烷之共聚物之組成物相比，該可固化聚矽氧組成物之觸變特性較差。 Patent Document 3 discloses a curable polysiloxane composition in Example 1, which includes: a combination of dimethylsiloxane and diphenylsiloxane terminated with trivinylsiloxy groups at two molecular chain ends. Copolymer; organopolysiloxane resin composed of CH 2 =CH(CH 3 ) 2 SiO 1/2 units, (CH 3 ) 3 SiO 1/2 units, and SiO 4/2 units; composed of (CH 3 ) 2 Polymethylhydrogensiloxane composed of HSiO 1/2 units and SiO 4/2 units; methylhydrogenpolysiloxane terminated with trimethylsiloxy groups at both molecular chain ends; platinum catalyst; Smoked silica; and organopolysiloxane with glycidoxypropyl group as thixotropy imparting agent. The curable polysiloxane composition cures to form a transparent cured product, but uses dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both molecular chain ends instead of dimethylsiloxane. Compared with the composition of the copolymer of diphenylsiloxane, the curable polysiloxane composition has poor thixotropic properties.
專利文件4於實例中揭示可固化聚矽氧組成物，其包含：在兩個分子鏈端處用二甲基乙烯基矽氧基封端之二甲基矽氧烷及二苯基矽氧烷之共聚物；由(CH 3) 3SiO 1/2單元、CH 2=CH(CH 3)SiO 2/2單元、及SiO 4/2單元組成之有機聚矽氧烷樹脂；由(CH 3) 2HSiO 1/2單元及SiO 4/2單元組成之有機氫聚矽氧烷；或在兩個分子鏈端處用三甲基矽氧基封端之甲基氫矽氧烷及二甲基矽氧烷之共聚物；鉑催化劑；及煙霧二氧化矽。此等可固化聚矽氧組成物具有觸變特性且固化以形成透明固化產物。然而，有機聚矽氧烷樹脂需要含有R 2SiO 2/2單元，其中各R獨立地表示烯基，或可經鹵素取代之烷基。此外，以直鏈有機聚矽氧烷及有機聚矽氧烷樹脂之總量計，有機聚矽氧烷樹脂之量限於10至40質量%之範圍內。 先前技術文件 專利文件 Patent Document 4 discloses a curable polysiloxane composition in an example, which includes: dimethylsiloxane and diphenylsiloxane terminated with dimethylvinylsiloxy groups at two molecular chain ends. Copolymer; organopolysiloxane resin composed of (CH 3 ) 3 SiO 1/2 units, CH 2 =CH(CH 3 )SiO 2/2 units, and SiO 4/2 units; composed of (CH 3 ) 2 Organohydrogen polysiloxane composed of HSiO 1/2 units and SiO 4/2 units; or methylhydrogensiloxane and dimethylsiloxane terminated with trimethylsiloxy groups at both molecular chain ends Copolymers of oxane; platinum catalysts; and fumed silica. These curable polysiloxane compositions have thixotropic properties and cure to form transparent cured products. However, the organopolysiloxane resin needs to contain R 2 SiO 2/2 units, where each R independently represents an alkenyl group, or an alkyl group that may be substituted by halogen. In addition, based on the total amount of linear organopolysiloxane and organopolysiloxane resin, the amount of organopolysiloxane resin is limited to the range of 10 to 40% by mass. Prior art documents patent documents
專利文件1：美國專利申請公開案第2004/0116640 A1號 專利文件2：日本專利申請案公開案第2006-335857 A號 專利文件3：韓國專利申請公開案第10-2009-0103785 A號 專利文件4：韓國專利申請公開案第10-2015-0065672 A號 Patent document 1: U.S. Patent Application Publication No. 2004/0116640 A1 Patent document 2: Japanese Patent Application Publication No. 2006-335857 A Patent document 3: Korean Patent Application Publication No. 10-2009-0103785 A Patent document 4: Korean Patent Application Publication No. 10-2015-0065672 A
技術問題technical issues
本發明之目標是提供一種可固化聚矽氧組成物，儘管含有大量有機聚矽氧烷樹脂，但其具有極佳觸變特性且可固化以形成透明固化產物。 問題之解決方案 The object of the present invention is to provide a curable polysiloxane composition which, despite containing a large amount of organopolysiloxane resin, has excellent thixotropic properties and can be cured to form a transparent cured product. Solution to problem
本發明之可固化聚矽氧組成物包含： (A) 由以下平均單元式表示之有機聚矽氧烷樹脂： (R 1 3SiO 1/2) a(R 2R 1 2SiO 1/2) b(SiO 4/2) c(HO 1/2) d其中各R 1獨立地係烷基；R 2係烯基；且「a」、「b」、「c」、及「d」係滿足以下條件之數值：a ≥ 0，b ＞ 0，0.3 ≤ c ≤ 0.7，0 ≤ d ≤ 0.05，且a + b + c = 1； (B) 在25℃下之黏度不大於1,000 mPa·s且選自以下之有機矽氧烷寡聚物：(B 1)在分子中具有至少一個矽原子鍵結烯基及至少一個矽原子鍵結芳基的有機矽氧烷寡聚物；(B 2)在分子中具有至少一個矽原子鍵結氫原子及至少一個矽原子鍵結芳基的有機矽氧烷寡聚物；及組分(B 1)與組分(B 2)之混合物； (C) 選自以下的有機聚矽氧烷：(C 1)在分子中具有至少一個烯基且不具有矽原子鍵結芳基及SiO 4/2單元的有機聚矽氧烷；(C 2)在分子中具有至少一個矽原子鍵結氫原子且不具有矽原子鍵結芳基的有機聚矽氧烷；及組分(C 1)與組分(C 2)之混合物； (D) 二氧化矽填料；及 (E) 催化量之矽氫化反應催化劑； 其中組分(A)之量在40.0至65.0質量%之範圍內，組分(B)之量在1.0至55.0質量%之範圍內，且組分(C)之量在0至50.0質量%之範圍內，各自以組分(A)至組分(C)之總質量計，且組分(D)之量相對於100質量份之組分(A)至組分(C)之總質量而在1至10質量份之範圍內，其限制條件為組分(A)至組分(C)中所有矽原子鍵結氫原子相對於所有矽原子鍵結烯基的莫耳比在0.5至2.0之範圍內。 The curable polysiloxane composition of the present invention includes: (A) Organopolysiloxane resin represented by the following average unit formula: (R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (SiO 4/2 ) c (HO 1/2 ) d wherein each R 1 is independently an alkyl group; R 2 is an alkenyl group; and "a", "b", "c", and "d" satisfy Values of the following conditions: a ≥ 0, b ＞ 0, 0.3 ≤ c ≤ 0.7, 0 ≤ d ≤ 0.05, and a + b + c = 1; (B) The viscosity at 25°C is not greater than 1,000 mPa·s and Organosiloxane oligomers selected from the following: (B 1 ) Organosiloxane oligomers having at least one silicon atom bonded to an alkenyl group and at least one silicon atom bonded to an aryl group in the molecule; (B 2 ) An organosiloxane oligomer having at least one silicon atom bonded to a hydrogen atom and at least one silicon atom bonded to an aryl group in the molecule; and a mixture of component (B 1 ) and component (B 2 ); (C) Organopolysiloxanes selected from the following: (C 1 ) Organopolysiloxanes having at least one alkenyl group in the molecule and not having silicon atoms bonded to aryl groups and SiO 4/2 units; (C 2 ) in the molecule Organopolysiloxane with at least one silicon atom bonded to a hydrogen atom and no silicon atom bonded to an aryl group; and a mixture of component (C 1 ) and component (C 2 ); (D) Silica filler ; and (E) a catalytic amount of silicon hydrogenation reaction catalyst; wherein the amount of component (A) is in the range of 40.0 to 65.0 mass%, the amount of component (B) is in the range of 1.0 to 55.0 mass%, and the composition The amount of component (C) is in the range of 0 to 50.0% by mass, each based on the total mass of component (A) to component (C), and the amount of component (D) is relative to 100 parts by mass of the component The total mass of (A) to component (C) is in the range of 1 to 10 parts by mass, and the limiting condition is that all silicon atoms bonded hydrogen atoms in component (A) to component (C) relative to all silicon The molar ratio of atoms bonded to alkenyl groups ranges from 0.5 to 2.0.
在各種實施例中，組分(B 1)係選自以下中之至少一者：(B 11)由以下通式表示之有機矽氧烷寡聚物： R 2R 3 2SiO(R 3 2SiO) mSiR 3 2R 2其中各R 2獨立地係烯基；各R 3獨立地係烷基或芳基，其限制條件為至少一個R 3係芳基；且「m」係0至10之整數，及 (B 12)由以下平均單元式表示之有機矽氧烷寡聚物： (R 2R 3 2SiO 1/2) e(R 3SiO 3/2) f其中R 2及R 3如上文所描述；且「e」及「f」係滿足以下條件之數值：e ＞ 0，f ＞ 0，且e + f = 1。 In various embodiments, component (B 1 ) is selected from at least one of: (B 11 ) an organosiloxane oligomer represented by the following general formula: R 2 R 3 2 SiO(R 3 2 SiO) m SiR 3 2 R 2 wherein each R 2 is independently alkenyl; each R 3 is independently alkyl or aryl, with the proviso that at least one R 3 is aryl; and "m" is 0 to 10 is an integer, and (B 12 ) is an organosiloxane oligomer represented by the following average unit formula: (R 2 R 3 2 SiO 1/2 ) e (R 3 SiO 3/2 ) f where R 2 and R 3 As described above; and "e" and "f" are values that satisfy the following conditions: e > 0, f > 0, and e + f = 1.
在各種實施例中，組分(B 11)係選自由下式表示之有機矽氧烷寡聚物中之至少一者： (CH 2=CH)(CH 3) 2SiO(C 6H 5) 2SiOSi(CH 3) 2(CH=CH 2) (CH 2=CH)(CH 3) 2SiO(C 6H 5)(CH 3)SiOSi(CH 3) 2(CH=CH 2) (CH 2=CH)(CH 3)(C 6H 5)SiOSi(CH 3)(C 6H 5)(CH=CH 2) 且組分(B 12)係由以下通用單元式表示之有機矽氧烷寡聚物： [(CH 2=CH)(CH 3) 2SiO 1/2] e[(C 6H 5)SiO 3/2] f其中「e」及「f」如上文所描述。 In various embodiments, component (B 11 ) is selected from at least one of the organosiloxane oligomers represented by the following formula: (CH 2 =CH)(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiOSi(CH 3 ) 2 (CH=CH 2 ) (CH 2 =CH)(CH 3 ) 2 SiO(C 6 H 5 )(CH 3 )SiOSi(CH 3 ) 2 (CH=CH 2 ) (CH 2 =CH)(CH 3 )(C 6 H 5 )SiOSi(CH 3 )(C 6 H 5 )(CH=CH 2 ) and component (B 12 ) is an organosiloxane oligosaccharide represented by the following general unit formula Polymer: [(CH 2 =CH)(CH 3 ) 2 SiO 1/2 ] e [(C 6 H 5 )SiO 3/2 ] f where "e" and "f" are as described above.
在各種實施例中，組分(B 2)係選自以下中之至少一者：(B 21)由以下通式表示之有機矽氧烷寡聚物： HR 3 2SiO(R 3 2SiO) mSiR 3 2H 其中各R 3獨立地係烷基或芳基，其限制條件為至少一個R 3係芳基；且「m」係0至10之整數，及 (B 22)由以下平均單元式表示之有機矽氧烷寡聚物： (R 3 2HSiO 1/2) e(R 3SiO 3/2) f其中R 3如上文所描述；且「e」及「f」係滿足以下條件之數值：e ＞ 0，f ＞ 0，且e + f = 1。 In various embodiments, component (B 2 ) is selected from at least one of: (B 21 ) an organosiloxane oligomer represented by the following general formula: HR 3 2 SiO(R 3 2 SiO) m SiR 3 2 H wherein each R 3 is independently an alkyl or aryl group, with the proviso that at least one R 3 is an aryl group; and "m" is an integer from 0 to 10, and (B 22 ) is represented by the following average units Organosiloxane oligomer represented by the formula: (R 3 2 HSiO 1/2 ) e (R 3 SiO 3/2 ) f wherein R 3 is as described above; and "e" and "f" satisfy the following conditions The values of: e ＞ 0, f ＞ 0, and e + f = 1.
在各種實施例中，組分(B 21)係選自由下式表示之有機矽氧烷寡聚物中之至少一者： H(CH 3) 2SiO(C 6H 5) 2SiOSi(CH 3) 2H H(CH 3) 2SiO(C 6H 5)(CH 3)SiOSi(CH 3) 2H 且組分(B 22)係由以下通用單元式表示之有機矽氧烷寡聚物： [(CH 3) 2HSiO 1/2] e[(C 6H 5)SiO 3/2] f其中「e」及「f」如上文所描述。 In various embodiments, component (B 21 ) is selected from at least one of the organosiloxane oligomers represented by the following formula: H(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiOSi(CH 3 ) 2 H H(CH 3 ) 2 SiO(C 6 H 5 )(CH 3 )SiOSi(CH 3 ) 2 H and component (B 22 ) is an organosiloxane oligomer represented by the following general unit formula: [ (CH 3 ) 2 HSiO 1/2 ] e [(C 6 H 5 )SiO 3/2 ] f where "e" and "f" are as described above.
在各種實施例中，可固化聚矽氧組成物進一步包含：(F)矽氫化反應抑制劑，相對於該組成物以質量單位計，其在此組分中的量係0.1至10,000 ppm。In various embodiments, the curable polysiloxane composition further includes: (F) a silicon hydrogenation reaction inhibitor in an amount in this component ranging from 0.1 to 10,000 ppm in mass units relative to the composition.
在各種實施例中，可固化聚矽氧組成物進一步包含：(G)助黏劑，相對於100質量份的組分(A)至組分(C)之總質量，其量係至多10重量份。 發明效果 In various embodiments, the curable polysiloxane composition further includes: (G) an adhesion promoter, in an amount of up to 10 parts by weight relative to 100 parts by mass of the total mass of component (A) to component (C). share. Invention effect
本發明之可固化聚矽氧組成物儘管含有大量有機聚矽氧烷樹脂，但具有極佳觸變特性且可固化以形成透明固化產物。 定義 Although the curable polysiloxane composition of the present invention contains a large amount of organopolysiloxane resin, it has excellent thixotropic properties and can be cured to form a transparent cured product. definition
用語「包含(comprising/comprise)」在本文中係以其最廣泛意義來使用，以意指並涵蓋「包括(including/include)」、「基本上由...所組成(consist(ing) essentially of)」、及「由...所組成(consist(ing) of)」之概念。使用「例如(for example)」、「例如(e.g.)」、「諸如(such as)」、及「包括(including)」來列示說明性實例不會只限於所列示之實例。因此，「例如」或「諸如」意指「例如，但不限於(for example, but not limited to)」或「諸如，但不限於(such as, but not limited to)」，且涵蓋類似或等效實例。本文中所使用之用語「約(about)」用來合理涵蓋或描述由儀器分析所測得之數值上的微小變化，或者由於樣本處理所致之數值上的微小變化。此等微小變化可係大約在數值之±0至25、±0至10、±0至5、或±0至2.5%內。此外，用語「約」當與值之範圍相關聯時，則適用於範圍之兩個數值。此外，即使在沒有明確陳述時，用語「約」亦可適用於數值。The term "comprising/comprise" is used herein in its broadest sense to mean and encompass "including/include", "consist(ing) essentially" of)", and the concept of "consist(ing) of)". The use of "for example," "e.g.," "such as," and "including" to list illustrative examples does not limit the scope of the stated examples. Therefore, "such as" or "such as" means "for example, but not limited to" or "such as, but not limited to" and covers similar or etc. Effective examples. The term "about" is used in this article to reasonably cover or describe small changes in values measured by instrumental analysis or due to sample processing. These small changes may be within approximately ±0 to 25, ±0 to 10, ±0 to 5, or ±0 to 2.5% of the numerical value. In addition, the term "about" when used in connection with a range of values applies to both values of the range. In addition, the term "about" may be applied to numerical values even when not expressly stated.
應當理解的是，所附申請專利範圍並不限於實施方式中所述之明確特定化合物、組成物、或方法，該等化合物、組成物、或方法可以在落入所附申請專利範圍之範疇內的特定實施例之間變化。關於本說明書中賴以描述各種實施例之特定特徵或態樣的馬庫西(Markush)群組，應瞭解到不同、特殊及/或非預期的結果可能自各別馬庫西群組的各成員獲得並且獨立於所有其他馬庫西成員。可個別及/或組合地依賴馬庫西組之各成員且對屬於隨附申請專利範圍之範疇內的特定實施例提供足夠支持。It should be understood that the patent scope of the appended application is not limited to the specific compounds, compositions, or methods described in the embodiments, and such compounds, compositions, or methods may fall within the scope of the appended patent application. vary between specific embodiments. Regarding the Markush Groups used to describe specific features or aspects of various embodiments in this specification, it should be understood that different, special and/or unexpected results may result from each member of the respective Markush Group Obtained and independent of all other Markusi members. Each member of the Markusi Group may be relied upon individually and/or in combination to provide sufficient support for specific embodiments falling within the scope of the appended claims.
亦應理解的是，描述本發明之各種實施例所依賴的任何範圍與次範圍皆獨立且共同落入隨附申請專利範圍之範疇中，並且將其理解為描述且預想到包括整體及/或其中部分值的所有範圍，即使此些值在本文中並未明白寫出。所屬技術領域中具有通常知識者可輕易認可的是，所列舉的範圍和子範圍充分描述並使本發明的各種實施例得以實行，並且這樣的範圍和子範圍可被進一步描述為相關的二等分、三等分、四等分、五等分等等。以下僅作為一個實例，「0.1至0.9 (of from 0.1 to 0.9)」的範圍可進一步分述為下三分之一（亦即0.1至0.30）、中三分之一（亦即0.4至0.6）、及上三分之一（亦即0.7至0.9），其個別且共同落入隨附申請專利範圍之範疇中，並且可被個別及/或共同地憑藉，而且會對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。另外，對於界定或修飾一個範圍之語言，諸如「至少(at least)」、「大於(greater than)」、「小於(less than)」、「不大於(no more than)」及其類似語言，應理解，此類語言包括子範圍及/或上限或下限。以下作為另一個實例，一「至少10 (at least 10)」的範圍自然包括至少10至35的子範圍、至少10至25的子範圍、25至35的子範圍等等，並且可個別及/或共同地憑藉各子範圍，而且會對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。最後，可憑藉落入所揭示範圍的個別數字，並且對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。舉例而言，「1至9 (of from 1 to 9)」的範圍包括各種個別整數如3、及包括小數點（或分數）的個別數字如4.1，其可被憑藉，並且對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。It is also to be understood that any ranges and subranges relied upon to describe various embodiments of the present invention are both independently and collectively within the scope of the appended claims and are to be understood as describing and contemplated to include the entirety and/or All ranges of some of these values, even if these values are not explicitly stated in this document. One of ordinary skill in the art will readily recognize that the enumerated ranges and subranges sufficiently describe and enable the practice of various embodiments of the invention, and that such ranges and subranges may be further described as relevant bisections, Thirds, fourths, fifths, etc. The following is just an example. The range of "0.1 to 0.9 (of from 0.1 to 0.9)" can be further divided into the lower third (that is, 0.1 to 0.30) and the middle third (that is, 0.4 to 0.6). , and the upper third (i.e., 0.7 to 0.9), which individually and jointly fall within the scope of the accompanying patent application, and can be relied upon individually and/or jointly, and will fall within the scope of the accompanying patent application Full support is provided by specific examples within the scope. In addition, for language that defines or modifies a range, such as "at least", "greater than", "less than", "no more than" and similar language, It is understood that such language includes subranges and/or upper or lower limits. As another example below, a range of "at least 10" naturally includes a sub-range of at least 10 to 35, a sub-range of at least 10 to 25, a sub-range of 25 to 35, etc., and may be individually and/or or collectively by virtue of the various sub-scopes, and will provide adequate support for specific embodiments falling within the scope of the appended claims. Finally, sufficient support may be given to specific embodiments falling within the scope of the disclosure and within the scope of the appended claims. For example, the range of "from 1 to 9" includes various individual integers such as 3, and individual numbers including decimal points (or fractions) such as 4.1, which can be relied upon and fall within the accompanying Full support is provided by specific examples within the scope of the claimed patent.
將詳細解釋本發明之可固化聚矽氧組成物。The curable polysiloxane composition of the present invention will be explained in detail.
組分(A)係由以下平均單元式表示之有機聚矽氧烷樹脂： (R 1 3SiO 1/2) a(R 2R 1 2SiO 1/2) b(SiO 4/2) c(HO 1/2) d。 Component (A) is an organopolysiloxane resin represented by the following average unit formula: (R 1 3 SiO 1/2 ) a (R 2 R 1 2 SiO 1/2 ) b (SiO 4/2 ) c ( HO 1/2 ) d .
在某些實施例中，各R 1獨立地係烷基。烷基之實例係具有1至12個碳原子之烷基，諸如甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一基、及十二基。其中，甲基係較佳的。 In certain embodiments, each R1 is independently alkyl. Examples of alkyl groups are alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl , cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Among them, the methyl series is preferred.
在該式中，R 2係烯基。烯基之實例係具有2至12個碳原子之烯基，諸如乙烯基、烯丙基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一烯基、及十二烯基。其中，乙烯基係較佳的。 In this formula, R 2 is alkenyl. Examples of alkenyl groups are alkenyl groups having 2 to 12 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, and dodecenyl. Among them, vinyl is preferred.
在該式中，「a」、「b」、「c」、及「d」係滿足以下條件之數值：a ≥ 0，b ＞ 0，0.3 ≤ c ≤ 0.7，0 ≤ d ≤ 0.05，及a + b + c = 1，可選地0.1 ≤ a ≤ 0.5，0.01 ≤ b ≤ 0.2，0.4 ≤ c ≤ 0.7，0 ≤ d ≤ 0.05，及a + b + c = 1，或可選地0.2 ≤ a ≤ 0.5，0.01 ≤ b ≤ 0.2，0.4 ≤ c ≤ 0.7，0 ≤ d ≤ 0.05，及a + b + c = 1。此係因為若「a」、「b」、「c」及「d」在上文所提及之範圍內的數值，則藉由固化本組成物所獲得之固化產物將具有適當硬度及機械強度。In this formula, "a", "b", "c", and "d" are values that satisfy the following conditions: a ≥ 0, b > 0, 0.3 ≤ c ≤ 0.7, 0 ≤ d ≤ 0.05, and a + b + c = 1, optionally 0.1 ≤ a ≤ 0.5, 0.01 ≤ b ≤ 0.2, 0.4 ≤ c ≤ 0.7, 0 ≤ d ≤ 0.05, and a + b + c = 1, or optionally 0.2 ≤ a ≤ 0.5, 0.01 ≤ b ≤ 0.2, 0.4 ≤ c ≤ 0.7, 0 ≤ d ≤ 0.05, and a + b + c = 1. This is because if "a", "b", "c" and "d" have values within the range mentioned above, the cured product obtained by curing the composition will have appropriate hardness and mechanical strength. .
用於組分(A)之有機聚矽氧烷樹脂之分子量不受限制，然而，其藉由凝膠滲透層析法(GPC)關於標準聚苯乙烯量測之數目平均分子量(Mn)較佳係至少1,500 g/mol、替代地至少2,000 g/mol，或替代地至少3,000 g/mol；而同時，Mn較佳地不大於6,000 g/mol；替代地不大於5,500 g/mol。組分(A)之Mn可係結合上述上限及下限的任意範圍。注意，若組分(A)在25℃下係固態，且難以均勻地混合本發明組成物中之其他組分，此可藉由預先製備組分(A)之有機溶液，且與一部分或所有組分(B)及組分(C)混合，之後可自此混合物移除所使用之有機溶劑。注意，可使用可用於製備組分(A)之有機溶液的有機溶劑，只要該有機溶劑可溶解組分(A)且容易移除即可。儘管不限於其，但其特定實例包括：芳族烴，諸如甲苯或二甲苯；及脂族烴，諸如己烷或庚烷。The molecular weight of the organopolysiloxane resin used in component (A) is not limited, however, its number average molecular weight (Mn) measured by gel permeation chromatography (GPC) with respect to standard polystyrene is preferred is at least 1,500 g/mol, alternatively at least 2,000 g/mol, or alternatively at least 3,000 g/mol; while at the same time, Mn is preferably not greater than 6,000 g/mol; alternatively not greater than 5,500 g/mol. The Mn of component (A) may be in any range combining the above upper and lower limits. Note that if component (A) is solid at 25°C and it is difficult to uniformly mix other components in the composition of the present invention, this can be done by preparing an organic solution of component (A) in advance and mixing it with part or all of the Component (B) and component (C) are mixed, and then the organic solvent used can be removed from the mixture. Note that an organic solvent that can be used to prepare the organic solution of component (A) can be used as long as the organic solvent can dissolve component (A) and is easily removed. Although not limited thereto, specific examples thereof include aromatic hydrocarbons such as toluene or xylene; and aliphatic hydrocarbons such as hexane or heptane.
組分(A)以40.0至65.0質量%之量，替代地以40.0至62.0質量%之量，替代地以45.0至65.0質量%之量，或替代地以45.0至62.0質量%之量使用，各自以組分(A)至組分(C)之總質量計。此係因為若量等於或高於上述範圍之下限，則藉由固化本組成物所獲得之固化產物將具有適當硬度及機械強度，然而該量等於或低於上述範圍之上限，該組成物在25℃下具有適當黏度。Component (A) is used in an amount of 40.0 to 65.0 mass%, alternatively 40.0 to 62.0 mass%, alternatively 45.0 to 65.0 mass%, or alternatively 45.0 to 62.0 mass%, respectively Based on the total mass of component (A) to component (C). This is because if the amount is equal to or higher than the lower limit of the above range, the cured product obtained by curing the composition will have appropriate hardness and mechanical strength. However, if the amount is equal to or lower than the upper limit of the above range, the composition will Appropriate viscosity at 25℃.
組分(B)係有機矽氧烷寡聚物，用以賦予可固化聚矽氧組成物觸變特性，且用以賦予藉由固化組成物所獲得之固化產物透明度。用於組分(B)之有機矽氧烷寡聚物之分子結構不受限制，然而，其實例係直鏈、部分支鏈直鏈、及支鏈。用於組分(B)之有機矽氧烷寡聚物之分子量不受限制，然而，其較佳地不大於2,000 g/mol，替代地不大於1,500 g/mol。此有機矽氧烷寡聚物典型地在25℃下之黏度不大於1,000 mPa·s，替代地不大於500 mPa·s，或替代地不大於100 mPa·s。注意，在本說明書中，黏度係使用B型黏度計根據ASTM D 1084在23 ± 2℃下量測之值。Component (B) is an organosiloxane oligomer, used to impart thixotropic properties to the curable polysiloxane composition, and to impart transparency to the cured product obtained by curing the composition. The molecular structure of the organosiloxane oligomer used in component (B) is not limited, however, examples thereof are linear chain, partially branched linear chain, and branched chain. The molecular weight of the organosiloxane oligomer used in component (B) is not limited, however, it is preferably not greater than 2,000 g/mol, alternatively not greater than 1,500 g/mol. The organosiloxane oligomer typically has a viscosity at 25°C of no greater than 1,000 mPa·s, alternatively no greater than 500 mPa·s, or alternatively no greater than 100 mPa·s. Note that in this manual, the viscosity is measured using a Type B viscometer in accordance with ASTM D 1084 at 23 ± 2°C.
用於組分(B)之有機矽氧烷寡聚物亦充當用於該組成物之鏈延伸劑及交聯劑，且係選自：(B 1)在分子中具有至少一個矽原子鍵結烯基及至少一個矽原子鍵結芳基的有機矽氧烷寡聚物；(B 2)在分子中具有至少一個矽原子鍵結氫原子及至少一個矽原子鍵結芳基的有機矽氧烷寡聚物；及組分(B 1)與組分(B 2)之混合物。 The organosiloxane oligomer used in component (B) also acts as a chain extender and cross-linking agent for the composition, and is selected from: (B 1 ) having at least one silicon atom bonded in the molecule Organosiloxane oligomers with alkenyl groups and at least one silicon atom bonded to an aryl group; (B 2 ) organosiloxanes with at least one silicon atom bonded to a hydrogen atom and at least one silicon atom bonded to an aryl group in the molecule Oligomers; and mixtures of component (B 1 ) and component (B 2 ).
用於組分(B 1)之有機矽氧烷寡聚物典型地係選自以下中之至少一者：(B 11)由以下通式表示之有機矽氧烷寡聚物： R 2R 3 2SiO(R 3 2SiO) mSiR 3 2R 2及(B 12)由以下平均單元式表示之有機矽氧烷寡聚物： (R 2R 3 2SiO 1/2) e(R 3SiO 3/2) f其中，組分(B 11)係較佳的。 The organosiloxane oligomer used in component (B 1 ) is typically selected from at least one of: (B 11 ) an organosiloxane oligomer represented by the following general formula: R 2 R 3 2 SiO(R 3 2 SiO) m SiR 3 2 R 2 and (B 12 ) are organosiloxane oligomers represented by the following average unit formula: (R 2 R 3 2 SiO 1/2 ) e (R 3 SiO 3/2 ) f Among them, component (B 11 ) is preferred.
在該式中，各R 2獨立係烯基，且其實例包括與上述基團相同的基團。其中，乙烯基係較佳的。 In this formula, each R 2 is independently an alkenyl group, and examples thereof include the same groups as the above-mentioned groups. Among them, vinyl is preferred.
在該式中，各R 3獨立地係烷基或芳基。R 3之烷基之實例包括與上述R 1相同之烷基。R 3之芳基之實例包括具有6至12個碳原子之芳基，諸如苯基、甲苯基、二甲苯基、及萘基。然而，至少一個R 3係芳基，典型係苯基。 In this formula, each R3 is independently an alkyl or aryl group. Examples of the alkyl group for R 3 include the same alkyl groups as for R 1 described above. Examples of aryl groups for R3 include aryl groups having 6 to 12 carbon atoms, such as phenyl, tolyl, xylyl, and naphthyl. However, at least one R 3 is an aryl group, typically phenyl.
在該式中，「m」係0至10之整數，替代地0至5之整數，替代地0至3之整數，或替代地0或1之整數。In this formula, "m" is an integer from 0 to 10, alternatively an integer from 0 to 5, alternatively an integer from 0 to 3, or alternatively an integer from 0 or 1.
在該式中，「e」及「f」係滿足以下條件之數值： e ＞ 0，f ＞ 0，且e + f = 1，替代地0.3 ＜ e且e + f = 1，或替代地0.5 ＜ e且e + f = 1。 In this formula, "e" and "f" are values that satisfy the following conditions: e > 0, f > 0, and e + f = 1, alternatively 0.3 < e and e + f = 1, or alternatively 0.5 < e and e + f = 1.
組分(B 1)通常係選自由下式表示之有機矽氧烷寡聚物中之至少一者： (CH 2=CH)(CH 3) 2SiO(C 6H 5) 2SiOSi(CH 3) 2(CH=CH 2) (CH 2=CH)(CH 3) 2SiO(C 6H 5)(CH 3)SiOSi(CH 3) 2(CH=CH 2) (CH 2=CH)(CH 3)(C 6H 5)SiOSi(CH 3)(C 6H 5) 2(CH=CH 2) 且組分(B 12)典型地係由以下通用單元式表示之有機矽氧烷寡聚物： [(CH 2=CH)(CH 3) 2SiO 1/2] e[(C 6H 5)SiO 3/2] f其中「e」及「f」如上文所描述。 Component (B 1 ) is usually selected from at least one of the organosiloxane oligomers represented by the following formula: (CH 2 =CH)(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiOSi(CH 3 ) 2 (CH=CH 2 ) (CH 2 =CH)(CH 3 ) 2 SiO(C 6 H 5 )(CH 3 )SiOSi(CH 3 ) 2 (CH=CH 2 ) (CH 2 =CH)(CH 3 )(C 6 H 5 )SiOSi(CH 3 )(C 6 H 5 ) 2 (CH=CH 2 ) and component (B 12 ) is typically an organosiloxane oligomer represented by the following general unit formula : [(CH 2 =CH)(CH 3 ) 2 SiO 1/2 ] e [(C 6 H 5 )SiO 3/2 ] f where "e" and "f" are as described above.
用於組分(B 2)之有機矽氧烷寡聚物通常係選自以下中之至少一者：(B 21)由以下通式表示之有機矽氧烷寡聚物： HR 3 2SiO(R 3 2SiO) mSiR 3 2H 及(B 22)由以下平均單元式表示之有機矽氧烷寡聚物： (R 3 2HSiO 1/2) e(R 3SiO 3/2) f其中，組分(B 21)係較佳的。 The organosiloxane oligomer used in component (B 2 ) is usually selected from at least one of the following: (B 21 ) An organosiloxane oligomer represented by the following general formula: HR 3 2 SiO( R 3 2 SiO) m SiR 3 2 H and (B 22 ) are organosiloxane oligomers represented by the following average unit formula: (R 3 2 HSiO 1/2 ) e (R 3 SiO 3/2 ) f where , component (B 21 ) is preferred.
在該式中，各R 3係烷基或芳基，且其實例包括與上述基團相同之基團。然而，至少一個R 3為芳基，典型係苯基。 In this formula, each R 3 is an alkyl group or an aryl group, and examples thereof include the same groups as the above-mentioned groups. However, at least one R 3 is an aryl group, typically phenyl.
在該式中，「m」係0至10之整數，替代地0至5之整數，替代地0至3之整數，或替代地0或1之整數。In this formula, "m" is an integer from 0 to 10, alternatively an integer from 0 to 5, alternatively an integer from 0 to 3, or alternatively an integer from 0 or 1.
在該式中，「e」及「f」係滿足以下條件之數值： e ＞ 0，f ＞ 0，且e + f = 1，替代地0.3 ＜ e且e + f = 1，或替代地0.5 ＜ e且e + f = 1。 In this formula, "e" and "f" are values that satisfy the following conditions: e > 0, f > 0, and e + f = 1, alternatively 0.3 < e and e + f = 1, or alternatively 0.5 < e and e + f = 1.
組分(B 21)通常係選自由下式表示之有機矽氧烷寡聚物中之至少一者： H(CH 3) 2SiO(C 6H 5) 2SiOSi(CH 3) 2H H(CH 3) 2SiO(C 6H 5)(CH 3)SiOSi(CH 3) 2H 且組分(B 22)典型地係由以下通用單元式表示之有機矽氧烷寡聚物： [(CH 3) 2HSiO 1/2] e[(C 6H 5)SiO 3/2] f其中「e」及「f」如上文所描述。 Component (B 21 ) is usually selected from at least one of the organosiloxane oligomers represented by the following formula: H(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiOSi(CH 3 ) 2 H H(CH 3 ) 2 SiO(C 6 H 5 )(CH 3 )SiOSi(CH 3 ) 2 H and component (B 22 ) is typically an organosiloxane oligomer represented by the following general unit formula: [(CH 3 ) 2 HSiO 1/2 ] e [(C 6 H 5 )SiO 3/2 ] f where "e" and "f" are as described above.
組分(B)以1.0至55.0質量%之量，替代地以1.0至50.0質量%之量，或替代地以1.0至45.0質量%之量使用，各自以組分(A)至組分(C)之總質量計。此係因為若量等於或高於上述範圍之下限，則組成物具有良好觸變特性，然而該量等於或低於上述範圍之上限，所獲得固化產物具有良好透明度。用於組分(B)之有機矽氧烷寡聚物可係組分(B 1)與組分(B 2)之混合物。然而，組分(B 1)及組分(B 2)之量不受限制，但組分(B)之量應係組分(A)至組分(C)中所有矽原子鍵結氫原子相對於所有矽原子鍵結烯基之莫耳比在0.5至2.0之範圍內的量。 Component (B) is used in an amount of 1.0 to 55.0% by mass, alternatively in an amount of 1.0 to 50.0% by mass, or alternatively in an amount of 1.0 to 45.0% by mass, each from component (A) to component (C) ) of the total mass. This is because if the amount is equal to or higher than the lower limit of the above range, the composition has good thixotropic properties, whereas if the amount is equal to or lower than the upper limit of the above range, the obtained cured product has good transparency. The organosiloxane oligomer used in component (B) may be a mixture of component (B 1 ) and component (B 2 ). However, the amounts of component (B 1 ) and component (B 2 ) are not limited, but the amount of component (B) should be all silicon atoms bonded to hydrogen atoms in component (A) to component (C). An amount in the range of 0.5 to 2.0 with a molar ratio of bonded alkenyl groups relative to all silicon atoms.
組分(C)係任意組分及選自以下之有機聚矽氧烷：(C 1)在分子中具有至少一個烯基且不具有矽原子鍵結芳基及SiO 4/2單元的有機聚矽氧烷；(C 2)在分子中具有至少一個矽原子鍵結氫原子且不具有矽原子鍵結芳基的有機聚矽氧烷；及組分(C 1)與組分(C 2)之混合物。 Component (C) is any component and an organic polysiloxane selected from the following: (C 1 ) An organic polysiloxane with at least one alkenyl group in the molecule and no silicon atom-bonded aryl group and SiO 4/2 unit Siloxane; (C 2 ) an organopolysiloxane having at least one silicon atom bonded to a hydrogen atom in the molecule and no silicon atom bonded to an aryl group; and component (C 1 ) and component (C 2 ) mixture.
若組分(A)與組分(B)之混合物可完全固化，可選地添加組分(C)。然而，若混合物由於缺乏矽原子鍵結烯基而不能固化，則應添加組分(C 1)，然而若混合物由於缺乏矽原子鍵結氫原子而不能固化，則應添加組分(C 2)。此外，若藉由固化本組成物所獲得之固化產物係硬的，則應添加組分(C)作為鏈延伸劑，然而若藉由固化本組成物所獲得之固化產物係軟的，則應添加組分(C)作為交聯劑。 Component (C) is optionally added if the mixture of components (A) and (B) can be fully cured. However, if the mixture fails to cure due to the lack of silicon atoms bonded to the alkenyl groups, component (C 1 ) should be added, whereas if the mixture fails to cure due to the lack of silicon atoms bonded to the alkenyl groups, component (C 2 ) should be added . In addition, if the cured product obtained by curing the present composition is hard, component (C) should be added as a chain extender, whereas if the cured product obtained by curing the present composition is soft, then component (C) should be added. Component (C) is added as cross-linking agent.
組分(C 1)係在分子中具有至少一個烯基且不具有矽原子鍵結芳基及SiO 4/2單元的有機聚矽氧烷。烯基之實例包括具有2至12個碳原子之烯基，諸如乙烯基、烯丙基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一烯基、及十二烯基。其中，乙烯基係較佳的。另外，組分(C 1)中除烯基以外之鍵結至矽原子之基團的實例包括具有1至12個碳原子之烷基，諸如甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一基、及十二基。 Component (C 1 ) is an organopolysiloxane having at least one alkenyl group in the molecule and not having silicon atoms bonded to aryl groups and SiO 4/2 units. Examples of alkenyl groups include alkenyl groups having 2 to 12 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, and dodecenyl. Among them, vinyl is preferred. In addition, examples of groups other than alkenyl groups bonded to silicon atoms in component (C 1 ) include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
組分(C 1)之分子結構不受限制，但典型係直鏈結構、部分支鏈直鏈結構、支鏈鏈結構、或環狀結構。組分(C 1)可係一種類型之具有此等分子結構的有機聚矽氧烷，或可係二或更多種類型之具有此等分子結構的有機聚矽氧烷的混合物。 The molecular structure of component (C 1 ) is not limited, but is typically a straight chain structure, a partially branched straight chain structure, a branched chain structure, or a cyclic structure. Component (C 1 ) may be one type of organopolysiloxane having such a molecular structure, or may be a mixture of two or more types of organopolysiloxane having such a molecular structure.
此組分(C 1)之實例包括在兩個分子鏈端處用二甲基乙烯基矽氧基封端之二甲基聚矽氧烷、在兩個分子鏈端處用二甲基乙烯基矽氧基封端之二甲基矽氧烷及甲基乙烯基矽氧烷之共聚物、在兩個分子鏈端處用三甲基矽氧基封端之二甲基矽氧烷及甲基乙烯基矽氧烷之共聚物、及其二或更多種類型之混合物。 Examples of this component (C 1 ) include dimethylpolysiloxane terminated with dimethylvinylsiloxy groups at both molecular chain ends, dimethylvinylsiloxane terminated with dimethylvinylsiloxy groups at both molecular chain ends. Copolymer of siloxy-terminated dimethylsiloxane and methylvinylsiloxane, dimethylsiloxane and methyl group terminated with trimethylsiloxy groups at both molecular chain ends Copolymers of vinylsiloxane, and mixtures of two or more types thereof.
組分(C 2)係在分子中具有至少一個矽原子鍵結氫原子且不具有矽原子鍵結芳基的有機聚矽氧烷。組分(C 2)中鍵結至矽原子之基團的實例包括具有1至12個碳原子之烷基，諸如甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一基、及十二基。 Component (C 2 ) is an organopolysiloxane having at least one silicon atom bonded to a hydrogen atom and no silicon atom bonded to an aryl group in the molecule. Examples of groups bonded to silicon atoms in component (C 2 ) include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Tertiary butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
組分(C 2)之分子結構不受限制，但典型地係直鏈結構、部分支鏈直鏈結構、支鏈結構、環狀結構、或三維網狀結構。組分(C 2)可係一種類型之具有此等分子結構之有機聚矽氧烷，或可係二或更多種類型之具有此等分子結構之有機聚矽氧烷的混合物。 The molecular structure of component (C 2 ) is not limited, but is typically a straight chain structure, a partially branched straight chain structure, a branched chain structure, a cyclic structure, or a three-dimensional network structure. Component (C 2 ) may be one type of organopolysiloxane having such molecular structure, or may be a mixture of two or more types of organopolysiloxane having such molecular structure.
此組分(C 2)之實例包括在兩個分子鏈端處用三甲基矽氧基封端之甲基氫聚矽氧烷、在兩個分子鏈端處用三甲基矽氧基封端之二甲基矽氧烷及甲基氫矽氧烷之共聚物、在兩個分子鏈端處用二甲基氫矽氧基封端之二甲基聚矽氧烷、在兩個分子鏈端處用二甲基氫矽氧基封端之二甲基矽氧烷及甲基氫矽氧烷之共聚物、由(CH 3) 2HSiO 1/2單元及SiO 4/2單元組成之共聚物、由(CH 3) 2HSiO 1/2單元、(CH 3) 3HSiO 1/2單元、及SiO 4/2單元組成之共聚物、及其二或更多種類型之混合物。 Examples of this component (C 2 ) include methyl hydrogen polysiloxane blocked with trimethylsiloxy groups at both molecular chain ends, Copolymer of terminal dimethylsiloxane and methylhydrogensiloxane, dimethylpolysiloxane terminated with dimethylhydrogensiloxy groups at both molecular chain ends, Copolymer of dimethylsiloxane and methylhydrogensiloxane terminated with dimethylhydrogensiloxy group, copolymer composed of (CH 3 ) 2 HSiO 1/2 unit and SiO 4/2 unit Materials, copolymers composed of (CH 3 ) 2 HSiO 1/2 units, (CH 3 ) 3 HSiO 1/2 units, and SiO 4/2 units, and mixtures of two or more types thereof.
組分(C)之有機聚矽氧烷可係組分(C 1)與組分(C 2)之混合物。然而，組分(C)典型地在25℃下之黏度不大於1,000 mPa·s，替代地不大於500 mPa·s，或替代地不大於100 mPa·s。注意，在本說明書中，黏度係使用B型黏度計根據ASTM D 1084在23 ± 2℃下量測之值。 The organopolysiloxane of component (C) may be a mixture of component (C 1 ) and component (C 2 ). However, component (C) typically has a viscosity at 25°C of no greater than 1,000 mPa·s, alternatively no greater than 500 mPa·s, or alternatively no greater than 100 mPa·s. Note that in this manual, the viscosity is measured using a Type B viscometer in accordance with ASTM D 1084 at 23 ± 2°C.
組分(C)以0至55.0質量%之量，替代地以0.1至50.0質量%之量，或替代地以0.5至45.0質量%之量使用，各自以組分(A)至組分(C)之總質量計。此係因為若量等於或高於上述範圍之下限，則組成物具有良好觸變特性，然而該量等於或低於上述範圍之上限，該組成物具有良好透明度。用於組分(C)之有機矽氧烷寡聚物可係組分(C 1)與組分(C 2)之混合物。然而，組分(C 1)及組分(C 2)之量不受限制，但組分(C)之量應係組分(A)至組分(C)中所有矽原子鍵結氫原子相對於所有矽原子鍵結烯基之莫耳比在0.5至2.0之範圍內的量。 Component (C) is used in an amount of 0 to 55.0% by mass, alternatively in an amount of 0.1 to 50.0% by mass, or alternatively in an amount of 0.5 to 45.0% by mass, each from component (A) to component (C) ) of the total mass. This is because if the amount is equal to or higher than the lower limit of the above range, the composition has good thixotropic properties, whereas if the amount is equal to or lower than the upper limit of the above range, the composition has good transparency. The organosiloxane oligomer used in component (C) may be a mixture of component (C 1 ) and component (C 2 ). However, the amounts of component (C 1 ) and component (C 2 ) are not limited, but the amount of component (C) should be all silicon atoms bonded to hydrogen atoms in component (A) to component (C). An amount in the range of 0.5 to 2.0 with a molar ratio of bonded alkenyl groups relative to all silicon atoms.
組分(A)至組分(C)中所有矽原子鍵結氫原子相對於所有矽原子鍵結烯基之莫耳比（「SiH/Vi比」）在0.5至2.0之範圍內，替代地在0.5至1.5之範圍內，或替代地在0.8至1.5之範圍內。此係因為若莫耳定量等於或高於上述範圍之下限，則組成物可完全固化，且藉由固化本組成物所獲得之固化產物將具有適當硬度及機械強度，然而該莫耳比等於或低於上述範圍之上限，該固化產物具有良好熱穩定性。Alternatively, the molar ratio of hydrogen atoms bonded to all silicon atoms relative to alkenyl groups bonded to all silicon atoms ("SiH/Vi ratio") in components (A) to (C) is in the range of 0.5 to 2.0, alternatively In the range of 0.5 to 1.5, or alternatively in the range of 0.8 to 1.5. This is because if the molar basis weight is equal to or higher than the lower limit of the above range, the composition can be completely cured, and the cured product obtained by curing the composition will have appropriate hardness and mechanical strength, whereas the molar ratio is equal to or Below the upper limit of the above range, the cured product has good thermal stability.
組分(D)係賦予可固化聚矽氧組成物觸變特性之二氧化矽填料。組分(D)典型地係煙霧化或沉澱之二氧化矽填料，其BET表面積係至少50 m 2/g，替代地80至400 m 2/g，或替代地100至400 m 2/g。二氧化矽填料之表面可未經處理或經處理劑處理，該等處理劑諸如有機氯矽烷、有機烷氧基矽烷、有機矽烷、及有機矽氧烷寡聚物。 Component (D) is a silica filler that imparts thixotropic properties to the curable polysiloxane composition. Component (D) is typically an aerosolized or precipitated silica filler having a BET surface area of at least 50 m 2 /g, alternatively 80 to 400 m 2 /g, or alternatively 100 to 400 m 2 /g. The surface of the silica filler may be untreated or treated with treatment agents such as organochlorosilanes, organoalkoxysilanes, organosilanes, and organosiloxane oligomers.
用於組分(D)之二氧化矽填料係市售的。二氧化矽填料之實例包括購自Degussa Corporation之商標名為AEROSIL ™之煙霧二氧化矽，諸如AEROSIL ™R8200、R9200、R812、R812S、R972、R974、R805、R202；購自Cabot Corporation之商標名為CAB-O-SIL ™ND-TS、TS610、或TS710之煙霧二氧化矽；及購自Tokuyama Corporation之商標名為REOLOSIL ™之煙霧二氧化矽，諸如DM-10、DM-20S、DM-30、HM-30S、MT-10、PM-20L、QS-10、QS-20A、及QS-25C。 Silica fillers used in component (D) are commercially available. Examples of silica fillers include fumed silicas available from Degussa Corporation under the trade name AEROSIL ™ , such as AEROSIL ™ R8200, R9200, R812, R812S, R972, R974, R805, R202; available from Cabot Corporation under the trade name CAB-O-SIL ™ ND-TS, TS610, or TS710 fumed silica; and fumed silica purchased from Tokuyama Corporation under the brand name REOLOSIL ™ , such as DM-10, DM-20S, DM-30, HM-30S, MT-10, PM-20L, QS-10, QS-20A, and QS-25C.
以100重量份組分(A)至組分(C)之總質量計，組分(D)之量在1至10質量份之範圍內，替代地在2至10質量份之範圍內。此係因為若組分(D)之量等於或高於上述範圍之下限，則組成物具有極佳觸變特性且藉由固化本組成物所獲得之固化產物具有適當硬度及機械強度，然而該量等於或低於上述範圍之上限，該可固化聚矽氧組成物具有良好透明度。The amount of component (D) is in the range of 1 to 10 parts by mass, alternatively in the range of 2 to 10 parts by mass, based on 100 parts by weight of the total mass of component (A) to component (C). This is because if the amount of component (D) is equal to or higher than the lower limit of the above range, the composition has excellent thixotropic properties and the cured product obtained by curing the composition has appropriate hardness and mechanical strength. However, this If the amount is equal to or lower than the upper limit of the above range, the curable polysiloxane composition has good transparency.
組分(E)係用於促進本組成物之固化的矽氫化反應催化劑。用於組分(E)之矽氫化反應催化劑在所屬技術領域中為眾所皆知的且可商購。合適的矽氫化催化劑包括但不限於鉑族金屬，其包括鉑、銠、釕、鈀、鋨、或銥金屬或其有機金屬化合物及其任二或更多者之組合。組分(E)典型地係基於鉑之催化劑，使得本組成物之固化可顯著加速。基於鉑之催化劑之實例包括鉑細粉、氯鉑酸、氯鉑酸之醇溶液、鉑-烯基矽氧烷錯合物、鉑-烯烴錯合物及鉑-羰基錯合物，其中鉑-烯基矽氧烷錯合物係最典型的。Component (E) is a silicon hydrogenation reaction catalyst used to promote the curing of the present composition. Hydrosilylation catalysts for component (E) are well known in the art and are commercially available. Suitable hydrogenation catalysts include, but are not limited to, platinum group metals including platinum, rhodium, ruthenium, palladium, osmium, or iridium metal or organometallic compounds thereof, and combinations of any two or more thereof. Component (E) is typically a platinum-based catalyst, allowing the curing of the present composition to be significantly accelerated. Examples of platinum-based catalysts include platinum fine powder, chloroplatinic acid, alcoholic solutions of chloroplatinic acid, platinum-alkenylsiloxane complexes, platinum-olefin complexes, and platinum-carbonyl complexes, wherein platinum- Alkenylsiloxane complexes are the most typical.
在各種實施例中，組分(E)係矽氫化反應催化劑，該矽氫化反應催化劑包括鉑與低分子量有機聚矽氧烷之錯合物，該等錯合物包括1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷與鉑之錯合物。此等錯合物可微囊封於樹脂基質中。在具體實施例中，催化劑包括1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷與鉑之錯合物。In various embodiments, component (E) is a hydrosilylation catalyst comprising complexes of platinum and low molecular weight organopolysiloxanes, the complexes comprising 1,3-divinyl -Complex of 1,1,3,3-tetramethyldisiloxane and platinum. These complexes can be microencapsulated in a resin matrix. In a specific embodiment, the catalyst includes a complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and platinum.
適用於組分(E)之矽氫化催化劑的實例描述於例如美國專利第3,159,601號；第3,220,972號；第3,296,291號；第3,419,593號；第3,516,946號；第3,814,730號；第3,989,668號；第4,784,879號；第5,036,117號；及第5,175,325號及第EP 0 347 895 B號中。微囊封矽氫化反應催化劑及其製備方法例示於美國專利第4,766,176號及第5,017,654號中。Examples of suitable hydrosilylation catalysts for component (E) are described, for example, in U.S. Patent Nos. 3,159,601; 3,220,972; 3,296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; No. 5,036,117; and No. 5,175,325 and EP 0 347 895 B. Microencapsulated silicon hydrogenation reaction catalysts and preparation methods thereof are exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654.
本組成物中之組分(E)之量係促進本組成物之固化的有效量。具體而言，為了令人滿意地固化本組成物，就質量單位而言，組分(E)之含量典型地係組分(E)中催化金屬相對於本組成物之含量係約0.01至約500 ppm、替代地約0.01至約100 ppm、替代地約0.01至約50 ppm、替代地約0.1至約10 ppm的數量。The amount of component (E) in the composition is an effective amount to promote the curing of the composition. Specifically, in order to satisfactorily cure the present composition, the content of component (E) is typically about 0.01 to about 0.01 to about the content of the catalytic metal in component (E) relative to the present composition in terms of mass units An amount of 500 ppm, alternatively about 0.01 to about 100 ppm, alternatively about 0.01 to about 50 ppm, alternatively about 0.1 to about 10 ppm.
在各種實施例中，可固化聚矽氧組成物包含(F)矽氫化反應抑制劑以調整可固化聚矽氧組成物之固化速率。在某些實施例中，組分(F)包括但不限於：炔烴醇（諸如2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇、或2-苯基-3-丁炔-2-醇、1-乙炔基-環己-1-醇）；烯炔化合物（諸如3-甲基-3-戊烯-1-炔、或3,5-二甲基-3-己烯-1-炔）；或1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、1,3,5,7-四甲基-1,3,5,7-四己烯基環四矽氧烷、參[(1,1-二甲基-2-丙炔基)氧基]甲基矽烷、順丁烯二酸二烯丙酯或苯并三唑可作為可選組分併入本組成物中。In various embodiments, the curable polysiloxane composition includes (F) a silicon hydrogenation reaction inhibitor to adjust the curing rate of the curable polysiloxane composition. In certain embodiments, component (F) includes, but is not limited to: alkyne alcohols (such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3 -alcohol, or 2-phenyl-3-butyn-2-ol, 1-ethynyl-cyclohex-1-ol); enyne compounds (such as 3-methyl-3-pentene-1-yne, or 3,5-dimethyl-3-hexene-1-yne); or 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1 ,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, s[(1,1-dimethyl-2-propynyl)oxy]methane Silanes, diallyl maleate or benzotriazole may be incorporated into the present composition as optional components.
本組成物中組分(F)之量不受特定限制，但若包括，則相對於組成物以質量單位計，該組分(F)典型地在此組成物中係約1至約10,000 ppm之量、替代地約10至約5,000 ppm之量。此係因為當組分(F)之量大於或等於上述範圍之下限時，組成物之儲存穩定性良好，然而當組分(F)之量小於或等於上述範圍之上限時，該組成物在低溫度下之可固化性良好。The amount of component (F) in the composition is not particularly limited, but if included, component (F) is typically from about 1 to about 10,000 ppm in the composition in mass units relative to the composition. amounts, alternatively, amounts of about 10 to about 5,000 ppm. This is because when the amount of component (F) is greater than or equal to the lower limit of the above range, the storage stability of the composition is good. However, when the amount of component (F) is less than or equal to the upper limit of the above range, the composition has good storage stability. Good curability at low temperatures.
為了改良固化產物對固化期間所接觸之基底材料的黏著性，本組成物可含有(G)助黏劑。在某些實施例中，用於組分(G)之助黏劑典型地係在分子中具有至少一個鍵結至矽原子之烷氧基的有機矽化合物。此烷氧基之實例係甲氧基、乙氧基、丙氧基、丁氧基、及甲氧基乙氧基；而甲氧基係最典型的。此外，鍵結至此有機矽化合物之矽原子的非烷氧基之實例係經取代或未經取代單價烴基，諸如烷基、烯基、芳基、芳烷基、鹵化烷基、及類似者；含環氧基之單價有機基團，例如3-環氧丙氧基丙基(3-glycidoxypropyl)、4-環氧丙氧基丁基(4-glycidoxybutyl)、或類似的環氧丙氧基烷基；2-(3,4-環氧環己基)乙基、3-(3,4-環氧環己基)丙基、或類似的環氧環己基烷基；及4-環氧乙烷基丁基(4-oxiranylbutyl)、8-環氧乙烷基辛基(8-oxiranyloctyl)、或類似的環氧乙烷基烷基；含丙烯酸基之單價有機基團，諸如3-甲基丙烯醯氧基丙基及類似者；及氫原子。此有機矽化合物通常具有矽鍵結烯基或矽鍵結氫原子。此外，由於對各種類型的基底材料賦予良好黏著性的能力，此有機矽化合物通常在分子中具有至少一個含環氧基之單價有機基團。此類型的有機矽化合物之實例係有機矽烷化合物、有機矽氧烷寡聚物、及烷基矽酸酯。有機矽氧烷寡聚物或烷基矽酸酯的分子結構之實例係直鏈結構、部分支鏈結構、支鏈結構、環狀結構、及網狀結構。直鏈結構、支鏈結構、及網狀結構係典型的。此類型之有機矽化合物的實例係矽烷化合物，諸如3-環氧丙氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯基氧基丙基三甲氧基矽烷、及類似者；在分子中具有至少一個矽鍵結烯基或矽鍵結氫原子、及至少一個矽鍵結烷氧基的矽氧烷化合物；在分子中具有至少一個矽鍵結烷氧基的矽烷化合物或矽氧烷化合物與在分子中具有至少一個矽鍵結羥基及至少一個矽鍵結烯基的矽氧烷化合物的混合物；及聚矽酸甲酯、聚矽酸乙酯、及含環氧基的聚矽酸乙酯。In order to improve the adhesion of the cured product to the base material contacted during curing, the composition may contain (G) adhesion promoter. In certain embodiments, the adhesion promoter for component (G) is typically an organosilicon compound having at least one alkoxy group bonded to a silicon atom in the molecule. Examples of such alkoxy groups are methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy; methoxy being the most typical. Furthermore, examples of non-alkoxy groups bonded to the silicon atom of the organosilicon compound are substituted or unsubstituted monovalent hydrocarbon groups, such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, and the like; Monovalent organic groups containing epoxy groups, such as 3-glycidoxypropyl, 4-glycidoxybutyl, or similar glycidoxyalkanes base; 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, or similar epoxycyclohexylalkyl; and 4-oxiranyl Butyl (4-oxiranylbutyl), 8-oxiranyloctyl, or similar oxiranyloctyl; monovalent organic groups containing acrylic acid groups, such as 3-methacrylamide Oxypropyl and the like; and hydrogen atoms. This organosilicon compound usually has silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms. In addition, due to the ability to impart good adhesion to various types of base materials, the organosilicon compound usually has at least one monovalent organic group containing an epoxy group in the molecule. Examples of organosilicon compounds of this type are organosilane compounds, organosiloxane oligomers, and alkyl silicate esters. Examples of the molecular structure of the organosiloxane oligomer or alkyl silicate are a linear structure, a partially branched chain structure, a branched chain structure, a cyclic structure, and a network structure. Linear chain structures, branched chain structures, and network structures are typical. Examples of organosilicon compounds of this type are silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, and the like; siloxane compounds having at least one silicon-bonded alkenyl group or silicon-bonded hydrogen atom, and at least one silicon-bonded alkoxy group in the molecule; in A mixture of a silane compound or a siloxane compound having at least one silicon-bonded alkoxy group in the molecule and a siloxane compound having at least one silicon-bonded hydroxyl group and at least one silicon-bonded alkenyl group in the molecule; and polysilicic acid Methyl ester, polyethyl silicate, and epoxy-containing polyethyl silicate.
在本組成物中，組分(G)之量不受特定限制，但為實現對在固化期間接觸的基底材料的良好黏著性，該量典型地係100重量份組分(A)至組分(C)之總質量之至多10重量份。In the present composition, the amount of component (G) is not particularly limited, but in order to achieve good adhesion to the base material contacted during curing, the amount is typically 100 parts by weight of component (A) to component The total mass of (C) is at most 10 parts by weight.
本組成物在25℃下之折射率不受限制，但其典型地在1.415至1.470之範圍內。雖然本組成物在25℃下之黏度不受限制，但其典型地在10至200 Pa·s之範圍內，如在1/s之剪切速率下量測。本組成物之觸變指數不受限制，但其典型地在1.2至6.0之範圍內，替代地在1.2至5.5之範圍內，替代地在1.5至6.0之範圍內，替代地在1.5至5.5之範圍內，替代地在2.0至6.0之範圍內，或替代地在2.0至5.5之範圍內。此係因為若本組成物之觸變指數等於或高於上述範圍之下限，則本組成物將能夠在分配其之後保持其形狀，然而該觸變指數等於或低於上述範圍之上限，本組成物將能夠形成適當形狀，諸如凸透鏡形狀，且在分配其時。在本文中所使用的「觸變指數(thixotropic index)」係自使用心軸藉助於流變計量測的1/s及10/s之剪切速率下本組成物在25℃下之黏度比([1/s下之黏度] / [10/s下之黏度])計算。 實例 The refractive index of the present composition at 25°C is not limited, but it is typically in the range of 1.415 to 1.470. Although the viscosity of the present composition at 25°C is not limited, it is typically in the range of 10 to 200 Pa·s, as measured at a shear rate of 1/s. The thixotropic index of the present composition is not limited, but it is typically in the range of 1.2 to 6.0, alternatively in the range of 1.2 to 5.5, alternatively in the range of 1.5 to 6.0, alternatively in the range 1.5 to 5.5 within the range, alternatively within the range of 2.0 to 6.0, or alternatively within the range of 2.0 to 5.5. This is because if the thixotropic index of the composition is equal to or higher than the lower limit of the above range, the composition will be able to maintain its shape after dispensing it. However, if the thixotropic index is equal to or lower than the upper limit of the above range, the composition The object will be able to be formed into appropriate shapes, such as a lenticular shape, and when dispensed. The "thixotropic index" used in this article is derived from the viscosity ratio of the composition at 25°C at shear rates of 1/s and 10/s measured using a mandrel with the help of a rheometer. ([Viscosity at 1/s] / [Viscosity at 10/s]) calculation. Example
本發明之可固化聚矽氧組成物將於下文中使用實例及比較例來詳細描述。然而，本發明不限於下列實例之描述。 [凝膠滲透層析法(GPC)] The curable polysiloxane composition of the present invention will be described in detail below using examples and comparative examples. However, the present invention is not limited to the description of the following examples. [Gel permeation chromatography (GPC)]
使用來自Waters Corporation之Waters 2695分離模組及Waters 2414折射率偵測器(RID)收集組分(a1)及組分(a2)之GPC資料。使用三個(7.8乘300 mm) Styragel HR管柱（其中分子量分離範圍係100至4,000,000）及具有甲苯之Styragel保護管柱（4.6乘30 mm）作為管柱。將樣本製備為0.5 wt%甲苯溶液且經由0.45微米PTFE注射器過濾器過濾。使用每分鐘一毫升之流速，偵測器及管柱的溫度係45℃，注入體積係100微升，且運行時間係60分鐘。相對於覆蓋580至2,610,000之分子量範圍之線性聚苯乙烯標準計算數目平均分子量(Mn)。 [折射率] GPC data for component (a1) and component (a2) were collected using a Waters 2695 separation module and a Waters 2414 refractive index detector (RID) from Waters Corporation. Three (7.8 by 300 mm) Styragel HR columns (with a molecular weight separation range of 100 to 4,000,000) and a Styragel guard column (4.6 by 30 mm) with toluene were used as columns. Samples were prepared as 0.5 wt% toluene solutions and filtered through 0.45 micron PTFE syringe filters. A flow rate of one milliliter per minute was used, the detector and column temperature was 45°C, the injection volume was 100 microliters, and the run time was 60 minutes. Number average molecular weight (Mn) was calculated relative to linear polystyrene standards covering the molecular weight range of 580 to 2,610,000. [Refractive index]
根據標準DIN 51423，藉助於由ATAGO Co., Ltd.生產之阿貝折射計(abbe refractometer)在1013 mbar之大氣壓下在589 nm之波長下量測可固化聚矽氧組成物在25℃下之折射率。 [黏度] According to the standard DIN 51423, the curable polysiloxane composition was measured at 25°C by means of an abbe refractometer produced by ATAGO Co., Ltd. at an atmospheric pressure of 1013 mbar and a wavelength of 589 nm. refractive index. [viscosity]
使用心軸#CP-40Z藉助於DV1 VISCOMETER (Brookfield)量測各有機矽氧烷寡聚物及有機聚矽氧烷在25℃下之黏度，保持1分鐘。 [觸變指數] The viscosity of each organosiloxane oligomer and organopolysiloxane was measured at 25°C using a DV1 VISCOMETER (Brookfield) using mandrel #CP-40Z and held for 1 minute. [Thixotropic index]
使用心軸（部件#543661.901，不鏽鋼，25 mm，2°，ETC錐形）藉助於ARES G2流變計(TA instrument)來量測可固化聚矽氧組成物在25℃下之黏度。量測1/s及10/s剪切速率下之黏度(Pa·s)，保持1分鐘。自1/s及10/s之剪切速率下之黏度比[1/s下之黏度]/[10/s下之黏度]計算觸變指數。 [硬度] The viscosity of the curable polysiloxane composition was measured at 25°C using a mandrel (part #543661.901, stainless steel, 25 mm, 2°, ETC cone) with the aid of an ARES G2 rheometer (TA instrument). Measure the viscosity (Pa·s) at shear rates of 1/s and 10/s and hold for 1 minute. The thixotropic index is calculated from the viscosity ratio [viscosity at 1/s]/[viscosity at 10/s] at shear rates of 1/s and 10/s. [hardness]
將可固化聚矽氧組成物倒入具有預定形狀之凹陷（厚度=10 mm）的模具中，且接著在150℃下固化1小時。藉助於由ASTM D2240指定之蕭氏A硬度計，藉助於D型硬度計硬度測試器及A型硬度計硬度測試器量測固化產物之硬度。 [透光率] The curable polysiloxane composition was poured into a mold with a predetermined shaped depression (thickness = 10 mm), and then cured at 150°C for 1 hour. The hardness of the cured product is measured with the aid of the Shore A hardness tester specified by ASTM D2240, the D-type durometer hardness tester and the A-type durometer hardness tester. [Transmittance]
將可固化聚矽氧組成物倒入模具（厚度=1 mm）中，且夾在載玻片玻璃（Matsunami Glass Co., Ltd.，產品#9213）之間。將經組裝之樣本在190℃下固化30 min。藉由ASTM D 1003中指定之方法（UV-可見光譜儀，Konica Minolta CM-3600A，參考=水）在室溫下量測在450 nm、550 nm、及700 nm波長下之透光率(%)。 [實例1至實例8及比較例1至比較例11] The curable polysiloxane composition was poured into a mold (thickness = 1 mm) and sandwiched between glass slides (Matsunami Glass Co., Ltd., product #9213). The assembled samples were cured at 190°C for 30 min. The light transmittance (%) at 450 nm, 550 nm, and 700 nm wavelengths was measured at room temperature by the method specified in ASTM D 1003 (UV-visible spectrometer, Konica Minolta CM-3600A, reference = water) . [Example 1 to Example 8 and Comparative Example 1 to Comparative Example 11]
將以下材料以表1至表4中所示之數量比例均勻混合以產生可固化聚矽氧組成物。當組分(A)在25℃下係固體時，藉由使用歸因於高黏度的溶劑，諸如甲苯及二甲苯而將該組分(A)添加至其他組分中。接著，為製備無溶劑組成物，使溶劑蒸發且用其他組分取代以促進混合。舉例而言，首先，將組分(B)添加至組分(A)溶解於溶劑中之溶液。接著，藉由用氮氣鼓泡加熱在減壓下移除溶劑。在冷卻至室溫之後，添加組分(C)。在室溫下混合混合物。另外，將其他組分添加至混合物中且在室溫下混合。如上文所提及，評估所得組成物及固化產物。此等結果在表1至表4中給出。表1至4中之各者中之「SiH/Vi比」指示組分(A)至組分(C)中所有矽原子鍵結氫原子相對於所有矽原子鍵結乙烯基之莫耳比。The following materials are uniformly mixed in the quantity ratios shown in Tables 1 to 4 to produce a curable polysiloxane composition. When component (A) is solid at 25°C, component (A) is added to other components by using solvents due to high viscosity, such as toluene and xylene. Next, to prepare a solvent-free composition, the solvent is evaporated and replaced with other components to facilitate mixing. For example, first, component (B) is added to a solution of component (A) dissolved in a solvent. Next, the solvent was removed under reduced pressure by heating with nitrogen bubbling. After cooling to room temperature, component (C) is added. Mix the mixture at room temperature. Additionally, other components were added to the mixture and mixed at room temperature. As mentioned above, the resulting composition and cured product were evaluated. These results are given in Tables 1 to 4. The "SiH/Vi ratio" in each of Tables 1 to 4 indicates the molar ratio of hydrogen atoms bonded to all silicon atoms to vinyl groups bonded to all silicon atoms in Component (A) to Component (C).
使用以下有機聚矽氧烷作為組分(A)。 (a1): 由以下平均單元式表示之有機聚矽氧烷樹脂： [(CH 3) 3SiO 1/2] 0.40[(CH 2=CH)(CH 3) 2SiO 1/2] 0.04(SiO 4/2) 0.56其具有約1.9質量%之乙烯基含量及約5,000之數目平均分子量(Mn)，且在25℃下係固體。 (a2): 由以下平均單元式表示之有機聚矽氧烷樹脂： [(CH 3) 3SiO 1/2] 0.40[(CH 2=CH)(CH 3) 2SiO 1/2] 0.10(SiO 4/2) 0.50其具有約3.0質量%之乙烯基含量及約3,000之數目平均分子量(Mn)，且在25℃下係固體。 The following organopolysiloxanes were used as component (A). (a1): Organopolysiloxane resin represented by the following average unit formula: [(CH 3 ) 3 SiO 1/2 ] 0.40 [(CH 2 =CH)(CH 3 ) 2 SiO 1/2 ] 0.04 (SiO 4/2 ) 0.56 It has a vinyl content of about 1.9% by mass and a number average molecular weight (Mn) of about 5,000, and is solid at 25°C. (a2): Organopolysiloxane resin represented by the following average unit formula: [(CH 3 ) 3 SiO 1/2 ] 0.40 [(CH 2 =CH)(CH 3 ) 2 SiO 1/2 ] 0.10 (SiO 4/2 ) 0.50 It has a vinyl content of about 3.0% by mass and a number average molecular weight (Mn) of about 3,000, and is solid at 25°C.
使用以下有機聚矽氧烷樹脂作為組分(A)之比較。 (a3): 由以下平均單元式表示之有機聚矽氧烷樹脂： [(CH 2=CH)(CH 3) 2SiO 1/2] 0.25(C 6H 5SiO 3/2) 0.75其具有5.62質量%之乙烯基含量，且在25℃下係固體。 (a4): 由以下平均單元式表示之有機聚矽氧烷樹脂： [(CH 3) 3SiO 1/2] 0.14[(CH 2=CH)(CH 3) 2SiO 1/2] 0.11(CH 3SiO 3/2) 0.53(C 6H 5SiO 3/2) 0.22其具有約2.2質量%之乙烯基含量，且在25℃下係固體。 The following organopolysiloxane resin was used for comparison of component (A). (a3): Organopolysiloxane resin represented by the following average unit formula: [(CH 2 =CH)(CH 3 ) 2 SiO 1/2 ] 0.25 (C 6 H 5 SiO 3/2 ) 0.75 which has 5.62 mass % vinyl content, and is solid at 25°C. (a4): Organopolysiloxane resin represented by the following average unit formula: [(CH 3 ) 3 SiO 1/2 ] 0.14 [(CH 2 =CH)(CH 3 ) 2 SiO 1/2 ] 0.11 (CH 3 SiO 3/2 ) 0.53 (C 6 H 5 SiO 3/2 ) 0.22 It has a vinyl content of approximately 2.2% by mass and is solid at 25°C.
以下有機矽氧烷寡聚物用作組分(B)。 (b1): 由下式表示之有機矽氧烷寡聚物： (CH 2=CH)(CH 3) 2SiO(C 6H 5) 2SiOSi(CH 3) 2(CH=CH 2) 且其具有8.7 mPa·s之黏度及約14.06質量%之乙烯基含量。 (b2): 由下式表示之有機矽氧烷寡聚物： H(CH 3) 2SiO(C 6H 5) 2SiOSi(CH 3) 2H 且其具有4.4 mPa·s之黏度及約0.61質量%之矽原子鍵結氫原子含量。 (b3): 由以下平均單元式表示之有機矽氧烷寡聚物： [(CH 3) 2HSiO 1/2] 0.60(C 6H 5SiO 3/2) 0.40且其具有29 mPa·s之黏度及約0.65質量%之矽原子鍵結氫原子含量。 The following organosiloxane oligomers were used as component (B). (b1): Organosiloxane oligomer represented by the following formula: (CH 2 =CH)(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiOSi(CH 3 ) 2 (CH=CH 2 ) and its It has a viscosity of 8.7 mPa·s and a vinyl content of approximately 14.06% by mass. (b2): Organosiloxane oligomer represented by the following formula: H(CH 3 ) 2 SiO(C 6 H 5 ) 2 SiOSi(CH 3 ) 2 H and having a viscosity of 4.4 mPa·s and about 0.61 Content of hydrogen atoms bonded to silicon atoms in mass %. (b3): Organosiloxane oligomer represented by the following average unit formula: [(CH 3 ) 2 HSiO 1/2 ] 0.60 (C 6 H 5 SiO 3/2 ) 0.40 and which has a pressure of 29 mPa·s Viscosity and silicon atom-bonded hydrogen atom content of approximately 0.65% by mass.
以下有機聚矽氧烷用作組分(B)之比較。 (b4): 由下式表示之有機聚矽氧烷： (CH 2=CH)(CH 3) 2SiO[(C 6H 5)(CH 3)SiO] 20Si(CH 3) 2(CH=CH 2) 且其具有2,300 mPa·s之黏度及約1.43質量%之乙烯基含量。 (b5): 由下式表示之有機聚矽氧烷： (CH 2=CH)(CH 3) 2SiO[(CH 3) 2SiO] 200[(C 6H 5) 2SiO] 50Si(CH 3) 2(CH=CH 2) 且其具有14,000 mPa·s之黏度及約0.22質量%之乙烯基含量。 The following organopolysiloxanes were used for comparison of component (B). (b4): Organopolysiloxane represented by the following formula: (CH 2 =CH)(CH 3 ) 2 SiO[(C 6 H 5 )(CH 3 )SiO] 20 Si(CH 3 ) 2 (CH= CH 2 ) and has a viscosity of 2,300 mPa·s and a vinyl content of approximately 1.43% by mass. (b5): Organopolysiloxane represented by the following formula: (CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 200 [(C 6 H 5 ) 2 SiO] 50 Si(CH 3 ) 2 (CH=CH 2 ) and has a viscosity of 14,000 mPa·s and a vinyl content of approximately 0.22% by mass.
以下有機聚矽氧烷用作組分(C)。 (c1): 由下式表示之有機聚矽氧烷： (CH 2=CH)(CH 3) 2SiO[(CH 3) 2SiO] 7Si(CH 3) 2(CH=CH 2) 且其具有7 mPa·s之黏度及約7.49質量%之乙烯基含量。 (c2): 由下式表示之有機聚矽氧烷： (CH 2=CH)(CH 3) 2SiO[(CH 3) 2SiO] 45Si(CH 3) 2(CH=CH 2) 且其具有60 mPa·s之黏度及約1.66質量%之乙烯基含量。 (c3): 由下式表示之有機聚矽氧烷： H(CH 3) 2SiO[(CH 3) 2SiO] 16Si(CH 3) 2H 且其具有15 mPa·s之黏度及約0.15質量%之矽原子鍵結氫原子含量。 (c4): 由以下平均單元式表示之有機聚矽氧烷樹脂： [(CH 3) 2HSiO 1/2] 0.65(SiO 4/2) 0.35且其具有23 mPa·s之黏度及約0.96質量%之矽原子鍵結氫原子含量。 The following organopolysiloxanes were used as component (C). (c1): Organopolysiloxane represented by the following formula: (CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 7 Si(CH 3 ) 2 (CH=CH 2 ) and its It has a viscosity of 7 mPa·s and a vinyl content of approximately 7.49% by mass. (c2): Organopolysiloxane represented by the following formula: (CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 45 Si(CH 3 ) 2 (CH=CH 2 ) and its It has a viscosity of 60 mPa·s and a vinyl content of approximately 1.66% by mass. (c3): Organopolysiloxane represented by the following formula: H(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 16 Si(CH 3 ) 2 H and having a viscosity of 15 mPa·s and about 0.15 Content of hydrogen atoms bonded to silicon atoms in mass %. (c4): Organopolysiloxane resin represented by the following average unit formula: [(CH 3 ) 2 HSiO 1/2 ] 0.65 (SiO 4/2 ) 0.35 and having a viscosity of 23 mPa·s and a mass of approximately 0.96 % of silicon atoms bonded hydrogen atom content.
以下煙霧二氧化矽用作組分(D)。 (d1): BET比表面積為230 m 2/g之煙霧二氧化矽（來自TOKUYAMA Corporation之REOLOSIL DM-30S） The following fumed silica was used as component (D). (d1): Smoked silica with a BET specific surface area of 230 m 2 /g (REOLOSIL DM-30S from TOKUYAMA Corporation)
以下矽氫化反應催化劑用作為組分(E)。 (e1): 含鉑與1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷之錯合物之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷溶液（鉑含量= 4質量%） The following hydrosilylation reaction catalyst was used as component (E). (e1): 1,3-Divinyl-1,1,3,3, a complex containing platinum and 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane -Tetramethyldisiloxane solution (platinum content = 4% by mass)
以下矽氫化反應抑制劑用作組分(F)。 (f1): 1-乙炔基-環己-1-醇 (f2): 1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷 The following hydrosilylation reaction inhibitors are used as component (F). (f1): 1-ethynyl-cyclohexan-1-ol (f2): 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane
以下助黏劑用作組分(G)。
(g1): 1,6-雙(三甲氧基矽基)己烷
(g2): 由以下平均單元式表示之有機聚矽氧烷樹脂：
[(CH
2=CH)(CH
3)
2SiO
1/2]
0.18(C
6H
5SiO
3/2)
0.54[CH
2(O)CHCH
2O(CH
2)
3SiO
3/2]
0.28［表1］
實例IE1至實例IE8係本文所述之可固化聚矽氧組成物之代表性實例，其展現具有透明度（在450 nm下之透光率＞ 99%）之觸變特性（觸變指數≥1.5）。如比較例CE2所示，在沒有組分(D)的情況下無法實現觸變特性。同時，比較例CE3及比較例CE4分別顯示在450 nm下之較低光學特性，96.39%及96.86%。當比較比較例CE4與實例IE5至實例IE8時，組分(B)之使用被認為賦予透明度並展現觸變特性。Examples IE1 to IE8 are representative examples of the curable polysiloxane compositions described herein, which exhibit thixotropic properties (thixotropic index ≥ 1.5) with transparency (transmittance at 450 nm > 99%) . As shown in Comparative Example CE2, thixotropic properties cannot be achieved without component (D). At the same time, Comparative Example CE3 and Comparative Example CE4 respectively showed lower optical properties at 450 nm, 96.39% and 96.86%. When comparing Comparative Example CE4 with Examples IE5 to IE8, the use of component (B) is believed to impart transparency and exhibit thixotropic properties.
根據比較例CE5，由於比較組分(b4)與組分(A)及組分(C)不相容，因此獲得非均質渾濁液體。比較例CE6至比較例CE9展示使用比較組分（比較組分a3、a4）及比較組分（比較組分b4、b5）之可固化聚矽氧組成物，其顯示在450 nm下小於99%之較低光學透光率。According to Comparative Example CE5, since the comparative component (b4) is incompatible with the component (A) and the component (C), a heterogeneous turbid liquid is obtained. Comparative Examples CE6 to Comparative Examples CE9 demonstrate curable polysiloxane compositions using comparative components (comparative components a3, a4) and comparative components (comparative components b4, b5), which exhibit a wavelength of less than 99% at 450 nm. The lower optical transmittance.
在比較例CE1之情況下，當使用65.06質量%的組分(a1)時，獲得過於黏性液體。 產業利用性 In the case of Comparative Example CE1, when 65.06% by mass of component (a1) was used, an excessively viscous liquid was obtained. Industrial applicability
本發明之可固化聚矽氧組成物儘管含有大量有機聚矽氧烷樹脂，但具有極佳觸變特性且可固化以形成透明固化產物。因此，可固化聚矽氧組成物可用於電氣/電子設備中之光學半導體元件的密封劑、黏著劑、或塗層。Although the curable polysiloxane composition of the present invention contains a large amount of organopolysiloxane resin, it has excellent thixotropic properties and can be cured to form a transparent cured product. Therefore, the curable polysiloxane composition can be used as a sealant, adhesive, or coating for optical semiconductor components in electrical/electronic equipment.
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